Forty Centuries of Ink Part 14

Der Getreue Schreibemeister (or True Writing Master), by Johann Friedr Vic.u.m, published in Dresden.

From 1602 to 1709 many "Indian" ink specimens were extant and are still of the different schools of penmanship. The productions of Phrysius, Materot and Barbedor ill.u.s.trating the French style, Vignon, Sellery and others, for the Italian hand, and Overbique and Smythers for the German text, and Ambrosius Perlengh and Hugo, with a few more, complete the list.

CHAPTER XII.

STUDY OF INK.

LACK OF INTEREST AS TO THE COMPOSITION OF INK DURING PART OF THE EIGHTEENTH CENTURY--THE CONDITIONS WHICH THEN PREVAILED NEARLY THE SAME AS THE PRESENT TIME--CHEMISTRY OF INK NOT UNDERSTOOD-- THIS LACK OF INFORMATION NOT CONFINED TO ANY PARTICULAR COUNTRY--LEWIS, IN 1765, BEGINS A SCIENTIFIC INVESTIGATION ON THE SUBJECT OF INKS --THE RESULTS AND HIS CONCLUSIONS PUBLISHED IN 1797--THE ROYAL SOCIETY OF ENGLAND IN 1787 RECEIVES COMPLAINTS ABOUT THE INFERIORITY OF INKS --ITS SECRETARY READS A PAPER THE SAME YEAR--THE PAPER CITED IN FULL--DR. BOSTOCK IN 1830 COMMUNICATES TO THE SOCIETY OF ARTS WHAT HE ESTIMATES TO BE THE CAUSES OF IMPERFECTIONS IN INK-- ACTION OF THE FRENCH ACADEMY OF SCIENCES-- COMPLICATIONS SURROUNDING THE MANUFACTURE OF INK ONLY THIRTY-FIVE YEARS AGO.

THE increasing demands for ink, and the lack of interest as to its composition during the eighteenth century, if viewed in the same lights which prevail in our own times, permitted the general manufacture of cheap grades of ink which possessed no very lasting qualities. The chemistry of Inks was not fully understood, indeed we find Professer Turner of the College of Edinburgh declaring in 1827:

"Gallic acid was discovered by Scheele in 1786, and exists ready formed in the bark of many trees, and in gall-nuts. It is always a.s.sociated with tannin, a substance to which it is allied in a manner hitherto unexplained. It is distinguished from tannin by causing no precipitate in a solution of gelatine. With a salt of iron it forms a dark blue coloured compound, which is the basis of ink. The finest colour is procured when the peroxide and protoxide of iron are mixed together. This character distinguishes gallic acid from every other substance excepting tannin."

The general lack of information or knowledge respecting ink chemistry or its time-phenomena was not confined to any particular country, and it does not appear that any general or specific attention was scientifically directed to it until 1765, when William Lewis, F. R. S., an English chemist, publicly announced that he proposed to investigate the subject.

His experimentations covered a period of many years and their results and his theories as to the phenomena of inks were published in 1797. The most valuable of his conclusions were that an excess of iron salt in the ink is detrimental to color permanence (such ink becoming brown on exposure) and also that acetic acid in the menstruum provides an ink of greater body and blackness than sulphuric acid does (a circ.u.mstance due to the smaller resistance of acetic acid to the formation of iron gallo-tannate). Many of his other observations were later shown to have been erroneous. Dr. Lewis was the first to advocate log- wood as a tinctorial agent in connection with iron and gall compositions.

Ribaucourt, a French ink maker, in 1798 determined that an excess of galls is quite as injurious to the permanence of ink as an excess of iron.

Pending the completion of the researches of Lewis, the Royal Society of England, affected by complaints from all quarters relative to the inferiority of inks as compared with those of earlier times, brought the subject to the attention of many of its members for discussion and advice. Its secretary, Charles Blagden, M. D., read a paper before the society, June 28, 1787, which was published in the "Philosophical Transactions"

and widely circulated. It is so interesting that copious extracts are given:

"In a conversation some time ago with my friend Thomas Astle, Esq., F. R. S. and A. S., relative to the legibility of ancient MSS. a question arose, whether the inks in use eight or ten centuries ago, which are often found to have preserved their colour remarkably well, were made of different materials from those employed in later times, of which many are already become so pale as scarcely to be read.

With a view to the decision of this question, Mr.

Astle obligingly furnished me with several MSS., on parchment and vellum, from the ninth to the fifteenth centuries inclusively, some of which were still black, and others of different shades of colour, from a deep yellowish brown to a very pale yellow, in some parts so faint as to be scarcely visible. On all of these I made experiments with the chemical re-agents which appeared to me best adapted to the purpose, namely, alkalis both simple and phlogisticated, the mineral acids, and infusions of galls.

"It would be tedious and superfluous to enter into a detail of the particular experiments, as all of them, one instance only excepted, agreed in the general result, to shew that the ink employed anciently, as far as the above-mentioned MSS.

extended, was of the same nature as the present; for the letters turned of a reddish or yellow brown with alkalis, became pale, and were at length obliterated, with the dilute mineral acids, and the drop of acid liquor which had extracted a letter, changed to a deep blue or green on the addition of a drop of phlogisticated alkali; moreover, the letters acquired a deeper tinge with the infusion of galls, in some cases more, in others less. Hence it is evident, that one of the ingredients was iron, which there is no reason to doubt was joined with the vitriolic acid; and the colour of the more perfect MSS. which in some was deep black, and in others purplish black, together with the rest.i.tution of that colour, in those which had lost it, by the infusion of galls, sufficiently proved that another of the ingredients was a stringent matter, which from history appears to be that of galls. No trace of a black pigment of any sort was discovered, the drop of acid which had completely extracted a letter, appearing of an uniform pale ferrugineous color, without an atom of black powder, or other extraneous matter, floating in it.

"As to the durability of the more ancient inks, it seemed, from what occurred to me in these experiments, to depend very much on a better preparation of the material upon which the writing was made, namely, the parchment or vellum; the blackest letters being those which had sunk into it deepest. Some degree of effervescence was commonly to be perceived when the acids came into contact with the surface of these old vellums. I was led, however, to suspect, that the more modern; for in general the tinge of colour, produced by the phlogisticated alkali in the acid laid upon them, seemed less deep; which, however, might depend in part upon the length of time they have been kept: and perhaps more gum was used in them, or possible they were washed over with some kind of varnish, though not such as gave gloss.

"One of the specimens sent me by Mr. Astle, of the fifteenth century, and the letters were those of an engrossing hand, angular, without any FINE strokes, broad and very black. On this none of the above-mentioned re-agents produced any considerable effect; most of them seemed to make the letters blacker, probably by cleaning the surface; and the acids, after having been rubbed strongly on the letters, did not strike any deeper tinge with the phlogisticated alkali. Nothing had a sensible effect toward obliterating these letters but what took off part of the surface of the vellum, when small rolls, as of a dirty matter, were to be perceived. It is therefore unquestionable, that no iron was used in this ink; and from its resistance to the chemical solvents, as well as a certain clotted appearance in the letters when examined closely, and in some places a slight degree of gloss, I have little doubt but they were formed with a composition of a black, sooty or carbonaceous powder and oil, probably something like our present printer's ink, and am not without suspicion that they were actually printed (a subsequent examination of a larger portion of this supposed MSS. has shown that it is really a part of a very ancient printed book).

"Whilst I was considering of the experiments to be made, in order to ascertain the composition of ancient inks, it occurred to me that perhaps one of the best methods of restoring legibility to decayed writing might be to join phlogisticated alkali with the remaining calx of iron, because, as the quant.i.ty of precipitate formed by these two substances very much exceeds that of the iron alone, the bulk of the colouring matter would thereby be greatly augmented. M. Bergman was of opinion that the blue precipitate contains only between a fifth and a sixth part of its weight of iron, and though subsequent experiments tend to show that, in some cases at least, the proportion of iron is much greater, yet upon the whole it is certainly true, that if the iron left by the stroke of a pen were joined to the colouring matter of phlogisticated alkali, the quant.i.ty of Prussian blue thence resulting would be much greater than the quant.i.ty of black matter originally contained in the ink deposited by the pen, though perhaps the body of colour might not be equally augmented. To bring the idea to the test, I made a few experiments as follows:

"The phlogisticated alkali was rubbed upon the bare writing in different quant.i.ties, but in general with little effect. In a few instances, however, it gave a bluish tinge to the letters, and increased their intensity, probably where something of an acid nature had contributed to the diminution of their colour.

"Reflecting that when phlogisticated alkali forms its blue precipitate with iron the metal is first usually dissolved in an acid, I was next induced to try the effect of adding a dilute mineral acid to writing besides the alkali. This answered fully to my expectations, the letters changing very speedily to a deep blue colour, of great beauty and intensity.

"It seems of little consequence as to the strength of colour obtained, whether the writing be first wetted with the acid, and then the phlogisticated alkali be touched upon it, or whether the process be inverted, beginning with the alkali; but on another account I think the latter way preferable. For the princ.i.p.al inconvenience which occurs in the proposed method of restoring MSS. is, that the colour frequently spreads, and so much blots the parchment as to detract greatly from the legibility; now this appears to happen in a less degree when the alkali is put on first, and the dilute acid is added upon it.

"The method I have hitherto found to answer best has been to spread the alkali thin with a feather or a bit of stick cut to a blunt point, though the alkali has occasioned no sensible change of colour, yet the moment that the acid comes upon it, every trace of a letter turns at once to a fine blue, which soon acquires its full intensity, and is beyond comparison stronger than the colour of the original trace had been. If now the corner of a bit of blotting paper be carefully and dexterously applied near the letters, in order to suck up the superfluous liquor, the staining of the parchment may be in a great measure avoided: for it is this superfluous liquor which absorbing part of the colouring matter from the letters becomes a dye to whatever it touches.

Care must be taken not to bring the blotting paper in contact with the letters, because the colouring matter is soft whilst wet, and may easily be rubbed off. The acid I have chiefly employed has been the marine; but both the vitriolic and nitrous succeed very well. They should undoubtedly be so far diluted as not to be in danger of corroding the parchment, after which the degree of strength does not seem to be a matter of much nicety.

"The method now commonly practiced to restore old writings, is by wetting them with an infusion of galls in white wine."

(See a complicated process for the preparation of such a liquor in Caneparius De Atramentis, A. D.

1660, p. 277)

"This certainly has a great effect; but is subject, in some degree, to the same inconvenience as the phlogisticated alkali, of staining the substance on which the writing was made. Perhaps if, instead of galls themselves, the peculiar acid of or other matter which strikes the black with iron were separated from the simple astringent matter, for which purpose two different processes are given by Piesenbring and by Scheele, this inconvenience might be avoided. It is not improbable, likewise, that a phlogisticated alkali might be prepared better suited to this object than the common; as by rendering it as free as possible from iron, diluting it to a certain degree, or subst.i.tuting the volatile alkali for the fixed. Experiment would most likely point out many other means of improving the process described above; but in its present state I hope it may be of some use, as it not only brings out a prodigious body of colour upon letters which were before so pale as to be almost invisible, but has the further advantages over the infusions of galls, that it produces its effect immediately, and can be confined to these letters only for which such a.s.sistance is wanted."

The Society of Arts in 1830, received a communication from Dr. Bostock, in the course of which he stated that the "tannin, mucilage and extractive matter are without doubt the princ.i.p.al causes of the difficulty which is encountered in the formation of a perfect and durable ink and for a good ink the essential ingredients are gallic acid and a sesqui salt of iron." Owing to his working with galls he was unable to make decisive experiments, but he concludes, and that rightly, that in proportion as ink consists merely of gallate of iron, it is less liable to decomposition and any kind of metamorphosis.

In 1831 the Academy of Sciences in France took up the matter and designated a committee composed of chemists with instructions to study the subject of a permanent ink. After long research it reported that it was unable to recommend any better ink than the tanno-gallate of iron one then in use, but "it should be properly compounded."

Peddington investigated, 1841-48, the ancient MSS.

collected by the Asiatic Society of Bengal, Calcutta, and published the results in "Examination of Some Decayed Oriental Works in the Library of the Asiatic Society," which are of much interest as relating to "mineral" inks, the "gall" inks being unknown in Asia after the twelfth century.

Up to thirty-five years ago, the manufacture of "gall" inks necessitated a complicated series of processes and long periods of time to enable the ink to settle properly, etc. It was Professor Penny of the Anderson University who suggested the way to avoid one of the processes pertaining to ink-making by utilizing the known fact, that tannin is more soluble in cold than in warm or hot water. It was adopted all over the world and revolutionized the manufacture of ink, by doing away with boiling processes and hot macerations of ingredients. With hardly in exception the best tanno-gallate of iron ("gall") inks are now "cold" made.

CHAPTER XIII.

STUDY OF INK.

INVESTIGATIONS BY STARK OF INK QUALITIES COVERING A PERIOD OF TWENTY-THREE YEARS--ABSTRACT FROM HIS REPORT OF 1855--DR. CHILTON EXPERIMENTS IN NEW YORK CITY 1856--ACTION OF THE PRUSSIAN GOVERNMENT IN 1859 AND EMPLOYMENT OF AN OFFICIAL INK--WATTENBACH'S GERMAN TREATISE ON THE ARCHIVES OF THE MIDDLE AGES--WILLIAM INGLIS CLARK ATTEMPTS TO PLACE THE MANUFACTURE OF INK ON A SCIENTIFIC BASIS--SUBMITS HIS VALUABLE RESEARCHES AND DEDUCTIONS TO THE ENINBURGH UNIVERSITY IN 1879--SCHLUTTIG AND NEUMANN IN 1890 ESTABLISH A STANDARD FORMULA FOR IRON AND GALL INK--NAMES OF SOME INK INVESTIGATORS OF THE NINETEENTH CENTURY.

DR. JAMES STARK, a famous chemist, submitted the results of twenty-three years of investigations of writing inks in a paper read by him in 1855 before the Society of Arts, in Edinburg, Scotland. The following is the abstract as printed by the London Artisan at the time:

"The author stated that in 1842 he commenced a series of experiments on writing inks, and up to this date (1855), had manufactured 229 different inks, and had tested the durability of writings made with these on all kinds of paper. As the result of his experiments be showed that the browning and fading of inks resulted from many causes, but in ordinary inks chiefly from the iron becoming peroxygenated and separating as a heavy precipitate. Many inks, therefore, when fresh made, yielded durable writings; but when the ink became old, the tanno-gallate of iron separated, and the durability of the ink was destroyed. From a numerous set of experiments the author showed that no salt of iron and no precipitate of iron equalled the common sulphate of iron--that is, the commercial copperas--for the purpose of ink- making; and that even the addition of any persalt, such as the nitrate or chloride of iron, though it improved the present color of the ink, deteriorated its durability. The author failed to procure a persistent black ink from manganese, or other metal or metallic salt. The author exhibited a series of eighteen inks which had either been made with metallic iron or with which metallic iron had been immersed, and directed attention to the fact that though the depth and body of color seemed to be deepened, yet in every case the durability of writings made with such inks was so impaired that they became brown and faded in a few months.

The most permanent ordinary inks were shown to be composed of the best blue gall nuts with copperas and gum, and the proportions found on experiment to yield the most persistent black were six parts of best blue galls to four parts of copperas.

Writings made with such an ink stood exposure to sun and air for twelve months without exhibiting any change of color, while those made with inks of every other proportion or composition had more or less of their color discharged when similarly tested. This ink, therefore, if kept from moulding and from depositing its tanno-gallate of iron, would afford writings perfectly durable. It was shown that no gall and logwood ink was equal to the pure gall ink in so far as durability in the writings was concerned. All such inks were exhibited which, though durable before the addition of logwood, faded rapidly after logwood was added to them. Sugar was shown to have an especially hurtful action on the durability of inks containing logwood--indeed, on all inks. Many other plain inks were exhibited, and their properties described --as gallo-sumach ink, myrabolams ink, Runge's ink, --inks in which the tanno-gallate of iron was kept in solution by nitric, muriatic, sulphuric, and other acids, or by oxalate of potash, chloride of lime, etc. The myrabolams was recommended as an ink of some promise for durability, and as the cheapest ink it was possible to manufacture. All ordinary inks, however, were shown to have certain drawbacks, and the author endeavored to ascertain by experiment whether other dark substances could be added to inks to impart greater durability to writings made with them, and at the same time prevent those chemical changes which were the cause of ordinary inks fading. After experimenting with various substances, and among others with Prussian blue and indigo dissolved in various ways, he found the sulphate of indigo to fulfil all the required conditions and, when added in the proper proportion to a tanno-gallate of iron ink, it yielded an ink which is agreeable to write with, which flows freely from the pen and does not clog it; which never moulds, which, when it dries on the paper, becomes of an intense pure black, and which does not fade or change its color however long kept. The author pointed out the proper proportions for securing those properties, and showed that the smallest quant.i.ty of the sulphate of indigo which could be used for this purpose was eight ounces for every gallon of ink. The author stated that the ink he preferred for his own use was composed of twelve ounces of gall, eight ounces of sulphate of indigo, eight ounces of copperas, a few cloves, and four or six ounces of gum arabic, for a gallon of ink.

It was shown that immersing iron wire or filings in these inks destroyed ordinary inks. He therefore recommended that all legal deeds or doc.u.ments should be written with quill pens, as the contact of steel invariably destroys more or less the durability of every ink. The author concluded his paper with a few remarks on copying inks and indelible inks, showing that a good copying ink has yet to be sought for, and that indelible inks, which will resist the pencilings and washings of the chemist and the forger, need never be looked for."

Professor Leonhardi, of Dresden, who had given much attention to the subject of inks, introduced in 1855 what he termed a NEW ink, and named it "alizarine ink," alizarin being a product obtained from the madder root, which he employed for "added" color in a tanno-gallate of iron solution. It possessed some merit due to its fluidity, and for a time was quite popular, but gradually gave place to the so-called chemical writing fluids; it is now obsolete.

Champour and Malepeyre, Paris, 1856, issued a joint manual, "Fabrication des Encres," devoted almost exclusively to the manufacture of inks and compiles many old "gall" and other ink formulas.

In 1856 Dr. Chilton of New York City published the results of ink experiments which he had made.

The accompanying extracts are taken from the local press of the month of April of that year:

"Some ingenious experiments to test the durability of writing inks have recently been made by Dr. Chilton, of New York City. He exposed a ma.n.u.script written with four different inks of the princ.i.p.al makers, of this and other countries, to the constant action of the weather upon the roof of his laboratory. After an exposure of over five months, the paper shows the different kind of writing in various shades of color. The English sample, Blackwood's, well known and popular from the neat and convenient way that it is prepared for this market, was quite indistinct.

"The American samples, David's, Harrison's and Maynard's are better. The first appears to retain its original shade very neatly; the two last are paler. This test shows conclusively the durability of ink; and while, for many purposes, school and the like, an ink that will stand undefaced a year or so, is all that is necessary, yet there is hardly a bottle of ink sold, some of which may not be used in the signature or execution of papers that may be important to be legible fifty or one hundred years hence.

"For state and county offices, probate records, etc., it is of vital importance that the records should be legible centuries hence. We believe that some of the early ma.n.u.scripts of New England are brighter than some town and church records of this century.

"In Europe at the present time, great care is taken by the different governments in the preparation of permanent ink--some of them even compounding their own, according to the most approved and expensive formulas.

"Ma.n.u.scripts of the eleventh and twelfth centuries now in the state paper office of Great Britain, are apparently as bright as when first written; while those of the last two hundred years are more or less illegible, and some of them entirely obliterated."

While the information sought to be conveyed in the last statement may be in some respects correct, it must be remembered that most of the MSS. extant dating before the thirteenth century were written in "Indian"

ink, while the great majority of those of the last two hundred years were not; and this fact alone would account to some extent for the differences mentioned.

The German (Prussian) government in 1859, as the result of an investigation, employed what they termed "Official Ink of the First Cla.s.s," i. e., a straight tanno- gallate of iron ink without added color; and if permanence were required as against removal by chemicals, it was accomplished by writing on paper saturated with chromates and ultramarine.